U.S. patent number 3,654,463 [Application Number 05/004,006] was granted by the patent office on 1972-04-04 for phosphorescent devices.
This patent grant is currently assigned to Bell Telephone Laboratories, Incorporated. Invention is credited to Joseph Edward Geusic, Frederick William Ostermayer, Jr., Le Grand Gerard Van Uitert.
United States Patent |
3,654,463 |
Geusic , et al. |
April 4, 1972 |
PHOSPHORESCENT DEVICES
Abstract
Incoherent light sources depending on phosphors which may
simultaneously emit at more than one wavelength are provided with
multiple dielectric coatings to suppress a portion of the emission
and thereby enhance the remainder. The use of such coatings with
frequency up-converting phosphors as well as down-converting
phosphors is described.
Inventors: |
Geusic; Joseph Edward (Berkeley
Heights, NJ), Ostermayer, Jr.; Frederick William (New
Providence, NJ), Van Uitert; Le Grand Gerard (Morris
Township, Morris County, NJ) |
Assignee: |
Bell Telephone Laboratories,
Incorporated (Murray Hill, NJ)
|
Family
ID: |
21708673 |
Appl.
No.: |
05/004,006 |
Filed: |
January 19, 1970 |
Current U.S.
Class: |
250/458.1;
250/486.1; 250/487.1 |
Current CPC
Class: |
C09K
11/025 (20130101); F21K 2/00 (20130101) |
Current International
Class: |
C09K
11/02 (20060101); F21K 2/00 (20060101); F21k
002/00 () |
Field of
Search: |
;250/71R,77,86
;350/311 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Borchelt; Archie R.
Assistant Examiner: Willis; Davis L.
Claims
We claim:
1. Incoherent phosphorescent emission source comprising a phosphor
adapted to at least partially transmit electromagnetic radiation of
different wavelengths, characterized in that said phosphor is
provided with a medium at least partially encompassing said
phosphor, said medium consisting essentially of at least two
successive layers, said layers being of such thicknesses and having
such refractive indices as to suppress one of the said wavelengths
relative to the other in which said phosphor is of such nature as
to produce at least one wavelength which is shorter that that of a
pump.
2. Source of claim 1 in which the wavelength of the said pump is in
the infrared spectrum.
3. Source of claim 2 in which the said pump is a forward biased,
gallium arsenide diode.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention is concerned with incoherent light sources utilizing
phosphor emission.
2. Description of the Prior Art
Incoherent light sources based on phosphor emission are already in
prevalent use and many new uses are contemplated. Such sources
depend upon a variety of pump means as, for example, electron
bombardment in cathode ray tubes; d.c. electric biasing in junction
devices, such as those using gallium arsenide; and light pumping as
in a variety of display devices. The latter category includes
higher frequency pumping in most common devices and lower frequency
pumping as in second photon devices. See Bulletin of the American
Physical Society, Series 11, Vol. 13, No. 4, p. 687, Paper HK7.
Phosphor materials are of many types, some inorganic, some organic;
some emit over rather narrow bandwidths, some over broad
bandwidths.
In any of the foregoing categories, a situation may arise in which
part of the pump energy is converted to undesired emission. This
undesired emission may be within or without the visible spectrum. A
specific example of recent concern has to do with second photon
sources utilizing long wavelength pumps. In one such example, a
forward biased GaAs diode is used to pump a rare earth-containing,
second photon phosphor to produce visible emission. Whereas such
devices operate efficiently at green and red wavelengths,
difficulty has been encountered in fabricating an efficient blue
source. In this particular example, a blue source is desired for
the construction of a three-color display system. While
thulium-containing materials (the initial absorption function being
performed by ytterbium) emit blue light when pumped by the infrared
emission from the diode, a significant part of the pump energy is
converted to a different wavelength of near infrared emission. As a
result, the efficiency of conversion to blue is diminished. Many
other similar examples exist.
A further complication resulting in inefficiency in phosphorescent
devices is concerned with inefficient utilization of pump energy.
In light-pumped devices, absorption coefficients for different
involved wavelengths may dictate different optimum thicknesses for
emission and for pump energy. Under some circumstances, for
example, dimension optimization for emission may result in
inefficient absorption of pump energy.
Problems similar to many of the foregoing were a deterrent to the
development of the laser. The problem there was largely one of
absorbing sufficient pump energy to create the required population
inversion. Resort was had to layered structures of various
dielectric films all individually transparent to wavelengths of
concern. Choice of thickness of two or more materials of
appropriate refractive indices results in constructive and
destructive interference at selected wavelengths.
This approach has permitted the design of a cavity which is
essentially totally resonant for the pump frequency. Energy of the
wavelength of concern may also be resonated so as to give the
required statistical number of passes for desired operation. See
Applied Optics and Optical Engineering, ed. R. Kingslake, Academic
Press, New York, 1965, Ch. 8.
SUMMARY OF THE INVENTION
In accordance with the invention, multilayered coatings of
transparent materials of critical thickness and refractive indices
partially or totally encompassing phosphor materials result in
suppression of energy of one or more wavelengths while permitting
transmission of energy of one or more other wavelengths. This is a
general solution which results in improvement of efficiency of
incoherent phosphorescent devices in any of the classes set forth
above. In certain embodiments, pumping efficiency is improved by
preventing escape of part of the pump energy or even by creating
resonant conditions for such pump energy. In the preferred
embodiment, significant improvement in emission is brought about by
suppression of one or more emission wavelengths to enhance at least
one other wavelength in phosphors having relevant emission
spectra.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is an energy level diagram in ordinate units of wavenumbers
for an appropriate second-photon phosphor system illustrative of
systems suitable for improvement in accordance with the inventive
principles;
FIG. 2 is a sectional view of a structure showing improved emission
efficiency in accordance with the invention;
FIG. 3 on coordinates of transmittance in percent, and wavelength
in microns illustrates the relationship of these coordinates for a
particular layered structure;
FIG. 4, in ordinate units of wavenumbers is an energy diagram
illustrating a down-converting phosphor system with multiple
emission lines, the efficiency of which may be improved in
accordance with the invention;
FIG. 5 is a sectional view of a phosphor layer dielectrically
coated in accordance with the invention; and
FIG. 6 is a sectional view of a portion of a structure alternative
to that of FIG. 5.
DETAILED DESCRIPTION
The invention has been generally described. The state of the
concerned arts is such that further description is unnecessary to
enable the person skilled in the art to practice the invention.
Suitable dielectric materials, relevant dielectric layer parameters
including refractive indices and thicknesses for accomplishment of
suppression and transmission as desired are available in the
literature. See for example Applied Optics and Optical Engineering,
ed. by R. Kingslake, Academic Press (1965), Vol.II, Ch. 8.
For illustrative purposes, a detailed description is set forth in
terms of the ytterbium-thulium, second-photon phosphor. This
particular system is of interest as a blue light source, for
example, as an indicator light or a portion of a display screen
with light pumping at a suitable infrared wavelength. Since
absorption is relatively narrow, this material is particularly
suitable for use with a narrow band emitting pump such as a laser
or a forward biased incoherent diode. The prime example of the
latter at this writing is the gallium arsenide diode.
1. Drawing
FIG. 1. In the ytterbium-thulium system (suitable hosts include
yttrium fluoride), infrared excited blue emission is produced by a
three-step sequential excitation. The efficiency of the infrared
excited blue emission from level 3 (all levels encircled on the
figure) is approximately 0.1 percent (i.e.
). At present, the blue emission is limited to this low value
because significant emission at 8,000 A. from level 2 occurs. In
fact, the emission from 8,000 A. is from 4 to 10 percent efficient.
A technique to improve the blue emission at the expense of the
8,000 A. emission is to provide a reflective coating on the
phosphor so as to effectively increase the radiative lifetime of
level 2, thus increasing the probability of excitation of atoms to
level 3 as compared to the probability of the 8,000 A. radiative
transition. In Tm, the 8,000 A. transition occurs to the ground
state; and in this case, if a coating of reflectivity R is used,
the effective radiative lifetime can be increased to
where .tau. is the normal radiative lifetime of the Tm.sup.3.sup.+
2 level. Since with multilayer coatings a reflectivity of greater
than 90 percent is easily achievable, emission at 4,800 A. (blue)
is increased by at least a factor of 10.
Several methods of entrapping the 8,000 A. radiation to improve the
blue emission are discussed in FIGS. 2 and 3. In FIG. 2 phosphor 1
such as YF.sub.3 :Yb,Tm is in the form of a thin transparent
coating on the diode 2 which may be Si-GaAs. The dome surface 3 of
the diode and the outer surface 4 of the phosphor have been coated
with a multilayer coating which is reflective at 8,000 A. and
transparent at 4,800 A.
A fifteen-layer coating which can be used is represented in FIG. 3.
The coating consists of a thirteen-layer,
1/4.lambda.(.lambda.=0.57.mu.), high and low index stack in which
the high index layer H.dbd.ZnS and the low index layer
L.dbd.MgF.sub.2. On either end, a 1/8.lambda. layer (H/2) of the
high index material is used. The general characteristic of such a
coating is also shown. If also the coatings are partially
reflective at the pump frequency (0.93.mu. for GaAs diodes) one can
get an even further enhancement because the intensity of the
0.93.mu. radiation in the phosphor is effectively increased by a
factor proportional to the number of internal reflections. The
enhancement of the efficiency of conversion to blue light (4,880
A.) is proportional to the N-1 power of the 0.93.mu. intensity
where N is the number of sequential photons involved providing
saturation effects have not been reached. N=3 for 0.480.mu.
emission.
Enhancement at 8,000 A is discussed. The coating is highly
reflecting at 4,880 A if the layers of the same dielectric
structure described above are 1/4.lambda. at 2,800 A. or 700 A.
thick. Such a coating reflects 4,800 A. and transmits 8,000 A. and
0.93.mu.. Thus the Tm phosphor can be used to pump YAG:Nd which
absorbs at 8,000 A. without undue loss as blue emission (4,880 A.).
Normal operation is 300 Amperes/cm.sup.2 in a GaAs diode.
Alternative ions emitting in the visible are Er, Ho. Devices are
again provided with coatings that reflect at all emission energies
save the one desired. It is important to provide suitable
reflection particularly for undesirable emissions having short
intrinsic radiative lifetimes.
Suitable host materials and other considerations germane to the
design of efficient light sources of the type described in
conjunction with FIG. 2 have been set forth elsewhere, see Applied
Physics Letters, Volume 15, No. 2, pages 48 to 54. Host materials
may be simple fluorides or more complex media shown to enhance
operation in accordance with a variety of mechanisms.
The energy diagram of FIG. 4 is illustrative of a more conventional
phosphor which emits at several wavelengths .lambda..sub.1,
.lambda..sub.2, and .lambda..sub.3 all longer than the pumping
wavelength. If any one of these fluorescences, say .lambda..sub.2,
is preferred, emission at that wavelength is improved by the
suppression of emission from the phosphor at the undesired
wavelengths .lambda..sub.1 and .lambda..sub.3 using multilayer
coatings on the phosphor which are highly reflective at the
undesired wavelengths and transmitting at the desired wavelength.
While the concept and the diagrams are general and apply to a large
number of conventional phosphors, a specific example is a phosphor
containing the active ion Er.sup.3.sup.+ in which case
.lambda..sub.p is a band of wavelengths from 0.5 - 0.4.mu. and
.lambda..sub.1 =0.55.mu., .lambda..sub.2 =0.65.mu. and
.lambda..sub.3 =0.82.mu.. For this case, the pump may be a
conventional Hg-Arc source.
FIG. 5 depicts a phosphor layer 10 covered by coatings 11 and 12.
Coating materials are selected in accordance with the
considerations set forth above.
In FIG. 6, the phosphor material 15 is particulate and each
particle is coated with multiple layers 16 to accomplish the end
described. While present techniques do not produce coatings of the
thickness uniformity which may be accomplished on massive smooth
surfaces, procedures are available for producing coatings which,
while they may not optimize, nevertheless improve emission
efficiency. Such techniques include evaporation, sputtering and
various other deposition techniques.
2. Design Requirements
The general requirement of the invention is that at least one
emitting surface of a phosphor be contacted by at least two layers
of materials of differing refractive indices so chosen as to
unequally suppress a portion of the spectrum relative to another
such portion. Suitable materials are necessarily transparent to all
concerned wavelengths, it being considered that an absorption of 5
percent at any concerned wavelength is the maximum permitted. The
number of layers, their indices and thickness, all depend on the
particular circumstances involved.
It is known that the applicable principles are those of
conventional filter design. Where it is desired to suppress or
transmit a relatively broad bandwidth to a relatively uniform
degree, a large number, for example fifteen or more layers may be
required. In less sophisticated devices where it may suffice merely
to suppress one or more relatively narrow bands and/or where flat
response is of little consequence, a smaller number of layers, as
few as two, may suffice.
* * * * *